The present invention relates to a curable composition comprising a saturated hydrocarbon polymer having a hydroxyl or hydrolyzable group bound to a silicon atom and a silicon-containing group capable of crosslinking via siloxane bonding (hereinafter referred to as xe2x80x9creactive silicon groupxe2x80x9d).
A saturated hydrocarbon polymer containing at least one reactive silicon group per molecule is known to have the interesting property that the hydrolysis of the reactive silicon group in the presence of, for example, moisture and subsequent formation of a siloxane bond give a rubber-like cured product. Because its backbone chain is composed of a saturated hydrocarbon which is scarcely susceptible to degradation by heat and light, this polymer is able to give a cured product having excellent heat resistance, wheathering resistance and gas barrier properties. Therefore, the polymer can be used as a sealing material for double glazing or an elastic sealant for architectural use.
For the curing by crosslinking of the polymer containing a reactive silicon group, a silanol condensation catalyst can be used. The use of a silanol condensation catalyst reduces the necessary cure time. Double glazing, in particular, is an article of commerce which calls for an extremely short delivery term and, therefore, the sealant for double glazing is much required to be fast-curing as a quality; hence there is a demand for a potent silanol condensation catalyst.
Japanese Kokai publication Hei-8-41360 discloses a curable composition utilizing a compound of the formula Q2Sn(OZ)2 or [Q2Sn(OZ)]2O (wherein Q represents a monovalent hydrocarbon group containing 1 to 20 carbon atoms; Z represents a monovalent hydrocarbon group containing 1 to 20 carbon atoms or an organic group internally having a functional group capable of coordinating with Sn) as a silanol condensation catalyst for expediting the cure of a saturated hydrocarbon polymer having a reactive silicon group. In the presence of such a curing catalyst, the curing reaction tends to proceed more rapidly than the reaction using a bivalent tin curing catalyst such as stannous octanoate or a tin carboxylate such as dibutyltin dilaurate. However, a further curtailment of cure time is necessary for a sealing agent for double glazing or other applications which require a very rapid curing.
As the technology utilizing an additive for accelerating the silanol condensation reaction of a reactive silicon group-containing saturated hydrocarbon polymer, Japanese Kokai publication Hei-2-97562 discloses a curable composition utilizing xe2x80x9ca polyhydroxymonosilane such that the number of hydroxyl groups bound to silicon atom is not less than 2 per moleculexe2x80x9d and Japanese Kokai publication Hei-2-196842 discloses a curable composition utilizing xe2x80x9ca silicon compound other than polysiloxane, in which the number of hydroxyl groups bound to a silicon atom is not less than 2 and there are 2 or more silicon atoms per moleculexe2x80x9d. Addition of such a silanol compound leads to improved curability but the effect is not satisfactory enough; hence there is a demand for a still more effective additive.
Meanwhile, sealing agents for double glazing are required to have the ability to adhere firmly to various adherends without application of a primer, that is to say the so-called non-primer adhesiveness. Recently, not only in the field of sealing materials for double glazing but also in the field of architectural sealants, the strong non-primer adhesiveness to various adherends is required for the improvement of work efficiency. However, the use of said reactive silicon group-containing saturated hydrocarbon polymer often resulted in an inadequate non-primer adhesion.
The present invention has for its object to provide a curable composition comprising a reactive silicon group-containing saturated hydrocarbon polymer which features a high curing rate and a high degree of adhesiveness to various adherends.
The inventors of the present invention carried out investigations with due diligence for solving the above-mentioned problems and found that the curing rate and adhesiveness of a composition can be improved without adversely affecting the physical properties of the cured product by adding a determined compound to a reactive silicon group-containing saturated hydrocarbon polymer.
The present invention, therefore, is concerned with a curable composition which comprises
(A) a saturated hydrocarbon polymer having at least one reactive silicon group,
(B) a tetravalent tin compound and
(C) a silicon compound represented by the formula
R1aSi(OR2)4-a 
xe2x80x83wherein R1 and R2 each independently represents a substituted or unsubstituted hydrocarbon group containing 1 to 20 carbon atoms; a represents any of 0, 1, 2 and 3.
The present invention is further concerned with a curable composition improved in both curing rate and adhesiveness, which comprises
(A) a saturated hydrocarbon polymer containing at least one reactive silicon group per molecule and having a molecular weight of 500 to 50,000 and, based on 100 weight parts thereof,
0.1 to 20 weight parts of (B) a tetravalent tin alcoholate and/or
0.02 to 20 weight parts of (C) a silicon compound of the formula
xe2x80x83R1aSi(OR2)4-a 
wherein R1 represents an aryl group containing 6 to 20 carbon atoms; R2 represents a substituted or unsubstituted hydrocarbon group containing 1 to 20 carbon atoms; and a represents any of 0, 1, 2 and 3.
The present invention is now described in detail.
The saturated hydrocarbon polymer for use in the present invention is a polymer substantially not containing carbonxe2x80x94carbon unsaturated bond other than an aromatic ring and, as such, includes polyethylene, polypropylene, polyisobutylene, hydrogenated polybutadiene, and hydrogenated polyisoprene, among others.
As the reactive silicon group, there can be mentioned a group of the general formula (2) 
(wherein R3 and R4 each independently represents an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, an aralkyl group containing 7 to 20 carbon atoms, or a triorganosiloxy group of the formula (Rxe2x80x2)3SiOxe2x80x94 (where Rxe2x80x2 groups each independently represents a substituted or unsubstituted hydrocarbon group containing 1 to 20 carbon atoms); X groups each independently represents a hydroxyl group or a hydrolyzable group; b represents any of 0, 1, 2 and 3; c represents any of 0, 1 and 2; provided, however, that both b and c are not simultaneously equal to 0; m represents an integer of 0 or 1 to 19).
As the hydrolyzable group, there can be mentioned the groups in routine use, such as hydrogen, alkoxy, acyloxy, ketoximate, amino, amido, aminooxy, mercapto and alkenyloxy, among others.
Among these, alkoxy, amido and aminooxy are preferred, although alkoxy is particularly preferred in view of its mild hydrolyzability and ease of handling.
The hydrolyzable and/or hydroxyl group may be attached, to 1 to 3 silicon atom(s), and (a+xcexa3b) is preferably 1 to 5. Where 2 or more hydrolyzable and/or hydroxyl groups bind to the reactive silicon group, they may be the same kind of group or different groups.
The number of silicon atoms forming the reactive silicon group is not less than 1 and where silicon atoms are linked by siloxane bonding or the like, the number of the silicon atoms is preferably not more than 20.
Particularly, the reactive silicon group represented by the general formula (4) is preferred from the standpoint of availability. 
(wherein R4, X and b are as defined hereinbefore)
The number of reactive silicon groups per molecule of the saturated hydrocarbon polymer is not less than 1, preferably 1.05 to 10, more preferably 1.1 to 5. If the number of reactive silicon groups per molecule is less than 1, curability will be insufficient so that a satisfactory rubber-like elasticity may not be realized.
The reactive silicon group may be located terminally and/or internally within the molecular chain of a saturated hydrocarbon polymer. Particularly, the reactive silicon group located at the terminal position within the molecule is preferred because the chain length between crosslinking sites of the saturated hydrocarbon polymer component in the cured product will then be increased so that a high-strength, high-elongation rubber-like cured product can be provided.
It should be understood that saturated hydrocarbon polymers containing such reactive silicon groups may be used each alone or in a combination of two or more species.
The polymer forming the backbone of the reactive silicon group-containing saturated hydrocarbon polymer to be used for the present invention can be obtained by (1) polymerizing an olefinic compound having 1 to 6 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene or the like, as a predominant monomer or (2) homo- or copolymerizing diene compounds, such as butadiene, isoprene or the like, or copolymerizing a diene compound with said olefinic compound(s) and hydrogenating the resulting copolymer. Isobutylene and hydrogenated polybutadiene polymers are preferred because they are more amenable to the introduction of a functional group into the terminus and easy to control its molecular weight and, in addition, the number of terminal functional groups can be increased.
The isobutylene polymer may be exclusively comprised of the isobutylene unit or may contain a monomer unit(s) copolymerizable with isobutylene up to the limit of preferably not more than 50% (weight %; the same applies hereinafter), more preferably not more than 30%, still more preferably not more than 10%.
As such monomer units, there can be mentioned olefins containing 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinylsilanes and allylsilanes, among others. As such copolymerizable component, there can be mentioned 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, xcex1-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, xcex2-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, xcex3-methacryloyloxypropyl-trimethoxysilane, and xcex3-methacryloyloxypropyl-methyldimethoxysilane.
When a vinylsilane or an allylsilane is used as said monomer copolymerizable with isobutylene, a group capable of functioning as a silane coupling agent can be introduced into the polymer so that the adhesiveness of the resulting composition can be improved.
In the hydrogenated polybutadiene polymer and other saturated hydrocarbon polymers, too, a vinylsilane or allylsilane compound can be incorporated in addition to the predominant monomer unit just as in the case of said isobutylene polymer.
The isobutylene polymer having a reactive silicon group for use in the present invention may contain a monomer unit which leaves a double bond after polymerization, such as a polyene compound, e.g. butadiene or isoprene, in a small amount within the range capable of accomplishing the object of the invention, i.e. preferably not more than 10%, more preferably not more than 5%, particularly not more than 1%.
The number average molecular weight of the saturated hydrocarbon polymer, preferably said isobutylene polymer or hydrogenated polybutadiene polymer, is preferably about 500 to 50,000, and polymers within the molecular weight range of about 1,000 to 30,000, which are either liquid or fluid, are more preferred from the standpoint of ease of handling.
The process for producing the reactive silicon group-containing saturated hydrocarbon polymer is now described.
Among isobutylene polymers having a reactive silicon group, an isobutylene polymer having a reactive silicon group at the molecular chain terminus can be produced using a polymer having a terminal functional group obtainable by the polymerization technique known as the inifer method (a cation polymerization method using a compound called xe2x80x9ciniferxe2x80x9d which doubles as an initiator and a chain transfer agent), preferably an isobutylene polymer having functional groups at all termini. Thus, an isobutylene polymer having a reactive silicon group can be obtained by the terminal dehydrohalogenation reaction of a polymer having a tertiary carbon-chlorine bond as obtained by a polymerization reaction or the terminal reaction of a polymer having a tertiary carbon-chlorine bond with allyltrimethylsilane to give a polyisobutylene having an unsaturated group terminally and subsequent addition reaction between the terminal unsaturated group and a hydrosilane compound of the general formula 
(wherein R3, R4, X, b, c and m are as defined hereinbefore) [this compound is a compound corresponding to the group of the general formula (2) to which a hydrogen atom has been attached], preferably a hydrosilane compound of the general formula 
(wherein R4, X and b are as defined hereinbefore) by using a platinum catalyst.
As the hydrosilane compound, there can be mentioned halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, etc.; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, etc.; and ketoximate silanes such as bis(dimethylketoximate)methylsilane, bis(cyclohexylketoximate) methylsilane, etc. Among these, halogenated silanes and alkoxysilanes are preferred.
Such production processes are described, for example, in Japanese Kokoku Publication Hei-4-69659, Japanese Kokoku Publication Hei-7-108928, Japanese Kokai Publication Sho-63-254149, Japanese Kokai Publication Sho-64-22904, and Japanese Patent Publication 2539445.
The isobutylene polymer having a reactive silicon group internally within its molecular chain can be produced by adding a vinylsilane or allylsilane having a reactive silicon group to an isobutylene-containing monomer and carrying out a copolymerization reaction.
Furthermore, an isobutylene polymer having reactive silicon groups both terminally and internally within its molecular chain can be produced by copolymerizing a vinylsilane or allylsilane having a reactive silicon group with an isobutylene monomer as a main component in the process for production of an isobutylene polymer having a terminal reactive silicon group and, then, introducing a reactive silicon group into the terminus of the resulting copolymer.
As the vinylsilane or allylsilane having a reactive silicon group, there may be mentioned vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, xcex3-methacryloyloxypropyltrimethoxysilane, and xcex3-methacryloyloxypropylmethyldimethoxysilane, among others.
Furthermore, as a further saturated hydrocarbon polymer having a reactive silicon group, other than said isobutylene polymer, a hydrogenated polybutadiene polymer having a reactive silicon group can be mentioned. The hydrogenated polybutadiene polymer having a reactive silicon group can be obtained by the hydrosilylation reaction of a hydrogenated polybutadiene polymer having an olefin group. The hydrogenated polybutadiene polymer having a terminal olefin group can be obtained by converting the hydroxyl group of a hydroxy-terminated hydrogenated polybutadiene polymer to an oxymetal group such as xe2x80x94ONa or xe2x80x94OK in the first place and reacting it with an organohalogen compound of the general formula (5):
CH2xe2x95x90CHxe2x80x94R5xe2x80x94Yxe2x80x83xe2x80x83(5)
[wherein Y represents a halogen atom such as chloride atom, bromide atom, or iodine atom; R5 represents a divalent organic group of the formula xe2x80x94R6xe2x80x94, xe2x80x94R6xe2x80x94OCOxe2x80x94 or xe2x80x94R6xe2x80x94COxe2x80x94 (where R6 represents a divalent hydrocarbon group containing 1 to 20 carbon atoms, preferably an alkylene, cycloalkylene, arylene or aralkylene group), more preferably a divalent group selected from the class consisting of xe2x80x94CH2xe2x80x94 and xe2x80x94Rxe2x80x3xe2x80x94C6H4xe2x80x94CH2xe2x80x94 (Rxe2x80x3 represents a hydrocarbon group of 1 to 10 carbon atoms)].
Conversion of the terminal hydroxyl group of the hydroxy-terminated hydrogenated polybutadiene polymer to an oxymetal group may for example be achieved by the reaction with an alkali metal, such as Na, K or the like; a metal hydride, such as NaH; a metal alkoxide, such as NaOCH3; or an alkali metal hydroxide, such as NaOH, KOH or the like.
By said method, an olefin-terminated hydrogenated polybutadiene polymer having a molecular weight close to that of the starting material hydroxy-terminated hydrogenated polybutadiene polymer is obtained. When a polymer having a higher molecular weight is to be produced, a polyvalent organohalogen compound containing 2 or more halogen atoms per molecule, such as methylene chloride, bis(chloromethyl)benzene, bis(chloromethyl)ether or the like, can be reacted prior to the reaction of said organohalogen compound of the general formula (5), whereby the molecular weight can be increased. By reacting the organohalogen compound of the general formula (5) thereafter, an olefin-terminated hydrogenated polybutadiene polymer having a greater molecular weight can be provided.
As a specific example of the organohalogen compound of the general formula (5), there can be mentioned allyl chloride, allyl bromide, vinyl(chloromethyl)benzene, allyl(chloromethyl)benzene, allyl(bromomethyl)benzene, allyl(chloromethyl)ether, allyl(chloromethoxy)benzene, 1-butenyl(chloromethyl)ether, 1-hexenyl-(chloromethoxy)benzene and allyloxy(chloromethyl)benzene. Among those compounds, allyl chloride is preferred because it is readily available and highly reactive.
As a method for introducing a reactive silicon group into said olefin-terminated hydrogenated polybutadiene polymer, a hydrosilylation reaction, like that mentioned for the production of an isobutylene polymer having a terminal reactive silicon group can be employed.
When the saturated hydrocarbon polymer having a reactive silicon group does not substantially contain any unsaturated bond other than an aromatic ring, a marked improvement in weathering resistance can be obtained as compared with sealants based on the conventional rubber-like polymers such as the unsaturated bond-containing organic polymers and oxyalkylene polymers. Moreover, being a hydrocarbon polymer, said polymer gives a cured product having good water resistance and low moisture permeability.
The proportion of the reactive silicon group-containing saturated hydrocarbon polymer in the curable composition of the present invention is preferably not less than 10%, more preferably not less than 20%, still more preferably not less than 30%.
As the component (B) of the curable composition of the present invention, a tetravalent tin compound, which is a silanol condensation catalyst having high activity, is employed.
As the tetravalent tin compound mentioned above, there can be mentioned tin carboxylates, dialkyltin oxides, and compounds of the general formula (3)
QdSn(OZ)4-d or [Q2Sn(OZ)]2Oxe2x80x83xe2x80x83(3)
(wherein Q represents a monovalent hydrocarbon group containing 1 to 20 carbon atoms; Z represents a monovalent hydrocarbon group containing 1 to 20 carbon atoms or an organic group internally containing a carbonyl group; d represents any of 0, 1, 2 and 3). In addition, the reaction product obtainable by reacting a tetravalent tin compound, such as a dialkyltin oxide, a dialkyltin diacetate or the like, with a low molecular weight silicon compound having a hydrolyzable silicon group, such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, or the like is also an effective curing catalyst capable of accelerating the silanol condensation reaction in a remarkable measure. Among these compounds, compounds of the general formula (3), namely chelate compounds, such as dibutyltin bisacetylacetonate, and tin alcoholates are preferred because of their high activity as silanol condensation catalysts. Particularly, the use of a tin alcoholate is preferred because the curing rate of the curable composition of the present invention is then dramatically increased and a sufficiently long pot life (the time allowable for the field work such as spatula-finishing after admixing of the main component with the curing agent) is also assured.
As the tin carboxylates mentioned above, there can be mentioned dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctanoate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin meleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, and dioctyltin diisooctylmalate.
As the dialkyltin oxide mentioned above, there can be mentioned dibutyltin oxide, dioctyltin oxide, and a mixture of dibutyltin oxide and a phthalic ester, among others.
As a specific example of the chelate compound mentioned above, there can be mentioned the following compounds; 
however it is not limited to these compounds.
As a specific example of the tin alcoholate mentioned above, there can be mentioned the following compounds; 
however it is not limited to these compounds.
Among these, dialkyltin dialkoxides are preferred. Dibutyltin dimethoxide, in particular, is most preferred in view of its high effectiveness and availability.
The component (B) in the present invention functions as a silanol condensation catalyst, and insofar as the object of the present invention can be accomplished, it may be used in combination with other silanol condensation catalysts. As such silanol condensation catalysts, there can be mentioned titanic esters such as tetrabutyl titanate, tetrapropyl titanate, etc.; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate, etc.; chelate compounds such as zirconium tetraacetylacetonate, titanium tetraacetylacetonate, etc.; lead octoate; amine compounds such as butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo(5.4.0)undecene-7 (DBU), etc., salts of such amine compounds with a carboxylic acid or the like; the low molecular weight polyamide resin obtainable from an excess of a polyamine and a polybasic acid; the reaction product of an excess of a polyamine with an epoxy compound; amino-containing silane coupling agents such as xcex3-aminopropyltrimethoxysilane, N-(xcex2-aminoethyl)aminopropylmethyldimethoxysilane, etc.; and other known silanol condensation catalysts inclusive of acid catalysts and basic catalysts, among others.
Those catalysts can be used each alone or in a combination of two or more species.
The formulating amount of said tetravalent tin compound as component (B) is preferably about 0.1 to 20 parts, more preferably 1 to 10 parts, relative to 100 parts of the saturated hydrocarbon polymer as component (A) (said parts are all by weight; the same applies hereinafter). If the formulating amount of said silanol condensation catalyst is below the above-specified range, the curing rate may decrease and the curing reaction will not proceed sufficiently in some instances. On the other hand, if the formulating amount of said silanol condensation catalyst exceeds this range, local generation of heat or foaming tends to take place in the course of curing so that a satisfactory cured product will hardly be obtained and, in addition, the pot life will be curtailed to interfere with field work.
For insuring a further enhancement of activity of the silanol condensation catalyst, an alkoxysilyl group-containing silicon compound of the general formula (1) is used as component (C) in the curable composition of the present invention.
R1aSi(OR2)4-a xe2x80x83xe2x80x83(1)
(wherein R1 and R2 each independently represents a substituted or unsubstituted hydrocarbon group containing 1 to 20 carbon atoms; a represents any of 0, 1, 2 and 3). The silicon compound of the general formula (1) has no silanol group. In this respect, the present invention is different from the inventions disclosed in Japanese Kokai publication Hei-2-97562 and Japanese Kokai publication Hei-2-196842 where silanol compounds are employed. It is generally acknowledged that a silanol group is higher in reactivity than an alkoxysilyl group and, for this reason, it has been thought that silanol compounds are preferred as cure accelerators. However, various investigations made by the present inventors revealed surprisingly that the above compound of the general formula (1) functions as an effective cure accelerator. One of the unique characteristics of the present invention resides in that such a compound as had not been considered to be an effective cure accelerator was found to be an effective cure accelerator to anybody""s surprise.
As a specific example of the silicon compound mentioned above, there can be mentioned the following specific compounds; 
however it is not limited to these compounds.
Among these, the compounds of the general formula (1) in which R1 is an aryl group having 6 to 20 carbon atoms, such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, etc. are preferred because of their high activity to accelerate the curing reaction of the composition. Particularly, diphenyldimethoxysilane and diphenyldiethoxysilane, which are inexpensive and readily available, are most preferred.
The formulating amount of this silicon compound as component (C) is preferably about 0.01 to 20 parts, more preferably 0.1 to 10 parts, relative to 100 parts of said saturated hydrocarbon polymer as component (A). If the formulating amount of the silicon compound is below this range, the cure accelerating effect will at times be decreased. On the other hand, if the formulating amount of said silicon compound exceeds this range, the hardness and tensile strength of the cured product are at times sacrificed.
The isocyanato-containing silane coupling agent as component (D) in the present invention is intended to enhance the adhesiveness between the adherend or substrate and the cured product of the reactive silicon group-containing saturated hydrocarbon polymer. The isocyanato-containing silane coupling agent is a compound having a group containing a silicon atom bound to a hydrolyzable group (hereinafter referred to as hydrolyzable silicon group) and an isocyanate group. As an example of said hydrolyzable silicon group, the group of the general formula (2) in which X is a hydrolyzable group can be mentioned. Specifically, the groups named hereinbefore as hydrolyzable groups can be mentioned but from the standpoint of the rate of hydrolysis, methoxysilyl, ethoxysilyl, etc. are preferred. The number of hydrolyzable groups is preferably not less than 2, more preferably not less than 3.
As the isocyanato-containing silane coupling agent mentioned above, there can be mentioned isocyanato-containing silanes such as xcex3-isocyanatopropyltrimethoxysilane, xcex3-isocyanatopropyltriethoxysilane, xcex3-isocyanatopropylmethyldiethoxysilane, xcex3-isocyanatopropylmethyldimethoxysilane and so forth.
The composition of the present invention may further comprise a silane coupling agent(s) other than said isocyanato-containing silane coupling agent as well as an tackifier other than silane coupling agents.
As a specific example of the silane coupling agents other than said isocyanato-containing silane coupling agent, there can be mentioned amino-containing silanes such as xcex3-aminopropyltrimethoxysilane, xcex3-aminopropyltriethoxysilane, xcex3-aminopropylmethyldimethoxysilane, xcex3-aminopropylmethyldiethoxysilane, xcex3-(2-aminoethyl)aminopropyltrimethoxysilane, xcex3-(2-aminoethyl)aminopropylmethyldimethoxysilane, xcex3-(2-aminoethyl)aminopropyltriethoxysilane, xcex3-(2-aminoethyl)aminopropylmethyldiethoxysilane, xcex3-ureidopropyltrimethoxysilane, N-phenyl-xcex3-aminopropyltrimethoxysilane, N-benzyl-xcex3-aminopropyltrimethoxysilane, N-vinylbenzyl-xcex3-aminopropyltriethoxysilane, etc.; mercapto-containing silanes such as xcex3-mercaptopropyltrimethoxysilane, xcex3-mercaptopropyltriethoxysilane, xcex3-mercaptopropylmethyldimethoxysilane, xcex3-mercaptopropylmethyldiethoxysilane, etc.; epoxy-containing silanes such as xcex3-glycidoxypropyltrimethoxysilane, xcex3-glycidoxypropyltriethoxysilane, xcex3-glycidoxypropylmethyldimethoxysilane, xcex2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, xcex2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, etc.; carboxysilanes such as xcex2-carboxyethyltriethoxysilane, xcex2-carboxyethylphenylbis(2-methoxyethoxy)silane, N-xcex2-(carboxymethyl)aminoethyl-xcex3-aminopropyltrimethoxysilane, etc.; vinyl unsaturated bond-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, xcex3-methacryloyloxypropylmethyldimethoxysilane, xcex3-acryloyloxypropylmethyltriethoxysilane, etc.; halogen-containing silanes such as xcex3-chloropropyltrimethoxysilane etc.; and isocyanurate silanes such as tris(trimethoxysilyl)isocyanurate and so froth. In addition, the modification derivatives of these compounds, such as amino-modified silyl polymers, silylated amino-containing polymers, unsaturated aminosilane complexes, phenylamino-long chain alkyl-silanes, aminosilylated silicones, silylated polyesters, etc. can also be used as silane coupling agents.
The isocyanato-containing silane coupling agent for use in the present invention is generally used in a proportion of 0.1 to 20 parts relative to 100 parts of the reactive silicon group-containing saturated hydrocarbon polymer. The preferred range is 0.5 to 10 parts. The isocyanato-containing silane coupling agents mentioned above may be used each alone or in a combination of two or more species.
The effect of the isocyanato-containing silane coupling agent formulated in the curable composition of the present invention is that when the composition is applied to various adherends, namely inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, etc. and organic substrates such as polyvinyl chloride, acryl, polyester, polyethylene, polypropylene, polycarbonate, etc., it brings about a marked improvement in adhesiveness, whether under non-primer conditions or under primer conditions. When it is used under non-primer conditions, the adhesiveness-improving effect with respect to various adherends is particularly remarkable.
In the curable composition of the present invention, various fillers are used where necessary. As a specific example of the fillers, there can be mentioned wood meal, pulp, cotton chip, asbestos, glass fiber, carbon fiber, mica, walnut shell flour, rice hull flour, graphite, diatomaceous earth, China clay, fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, aluminum dust, flint powder, zinc powder, etc. Among these fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide and talc are preferred. Those fillers can be used each alone or in a combination of two or more species. The proportion of the filler, if used, is preferably 10 to 1000 parts, more preferably 50 to 300 parts, relative to 100 parts of component (A).
The curable composition of the present invention is supplemented with various additives where necessary.
As an example of the additives mentioned above, there can be mentioned a modifier for adjusting the tensile characteristics of the cured product, a plasticizer, an antioxidant, a radical chain terminator, an ultraviolet absorber, a sequestrant, an ozone degradation inhibitor, a light stabilizer, a phosphorus type peroxide decomposer, a lubricant, a pigment, a blowing agent, a photocurable resin and a thixotropic agent.
The specific additive substances are described in the specifications of Japanese Kokoku Publication Hei-4-69659, Japanese Kokoku Publication Hei-7-108928, Japanese Kokai Publication Sho-63-254149 and Japanese Kokai Publication Sho-64-22904, among other publications.
The curing-improving effect attributable to the combined use of the tetravalent tin compound and the silicon compound of the general formula (1) in accordance with the present invention is expressed equally regardless of the presence or absence of the isocyanato-containing silane coupling agent as component (D) of the present invention. Moreover, this curing-improving effect is obtained when said various additives are added as well. Thus, in the application of the curable composition of the present invention as an architectural elastic sealant, a sealant for double glazing, an electric/electronic component sealant such as a solar battery back sealant or an electrical insulation, e.g. a conductor or cable sheathing, a pressure sensitive adhesive, an adhesive, or a rust preventive/water proof sealant for wire-mesh glass or double glazing edge (a section) treatment, the curing rate of such curable materials can be dramatically increased.